CN109517364A - A kind of colour ETPU sole and preparation method thereof - Google Patents
A kind of colour ETPU sole and preparation method thereof Download PDFInfo
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- CN109517364A CN109517364A CN201811415110.9A CN201811415110A CN109517364A CN 109517364 A CN109517364 A CN 109517364A CN 201811415110 A CN201811415110 A CN 201811415110A CN 109517364 A CN109517364 A CN 109517364A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2435/06—Copolymers with vinyl aromatic monomers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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Abstract
The invention discloses a kind of colour ETPU soles and preparation method thereof, are related to sole material technical field.The raw material of colored ETPU sole includes the component of following parts by weight: 10-20 parts of isoflurane chalcone diisocyanate；20-40 parts of polyester polyol；10-20 parts of polyether polyol；2-5 parts of chain extender；1-5 parts of white carbon black；Different 1-2 parts of Masterbatch mixture of at least two colors；The raw material of Masterbatch includes the component of following parts by weight: 25-30 parts of TPU；30-50 parts of pigment；1-5 parts of dispersing agent；0.5-1.5 parts of heat stabilizer；0.5-1.5 parts of light stabilizer；10-20 parts of filler；6-8 parts of compatilizer；6-10 parts of lubricant.Pigment is added in TPU base-material, and the compatibility that compatilizer increases pigment is added, the dispersibility of dispersing agent enhancing pigment is added, and heat stabilizer and light stabilizer can resist the photo-thermal oxidation of the benzene ring structure of polyurethane, jaundice avoided to influence TPU color；It is fast light, heat-resisting, oxidation resistent susceptibility is strong using isoflurane chalcone diisocyanate, it is not likely to produce xanthochromia, improves product quality.
Description
Technical field
The present invention relates to sole material technical fields, more specifically, it relates to a kind of colour ETPU sole and its preparation
Method.
Background technique
Major part foamed material is all to make plastics by the way that physics or chemical foaming agent is added using plastics as matrix at present
Intrinsic silicon obtains a large amount of bubble.Foamed material possesses the characteristics such as heat-insulated, damping and sound-absorbing due to its light specific gravity,
Therefore it is all had been widely used in fields such as daily necessities, packaging and automobiles.Thermoplastic polyurethane (TPU) can generally divide
For polyester and polyether-type, hardness range is very broad (50HA-80HD), and have excellent wear-resisting, high mechanical strength,
The advantages that good water-fast, oil resistant and fusible recycling.TPU foamed material not only remains the excellent of protocorm material
Performance, but also have good resilience, low-density and can be used within the scope of broad temperature.
Conventional TPU footwear material is typically white, in order to enrich the appearance of TPU footwear material, such as formed it is colored or
Secondary colour TPU footwear material needs that Masterbatch is just added when manufacturing ETPU particle, due to the poor compatibility of Masterbatch and TPU, can lead
Color drift is caused, the more difficult equilibrium of color reduces product quality.
Summary of the invention
In view of the deficienciess of the prior art, the purpose of the present invention one is to provide a kind of colour ETPU sole and its preparation
Method has the advantages that color is uniform, lucuriant in design.
The purpose of the present invention one is to provide a kind of preparation method of colour ETPU sole, using the sole of this method preparation
Have the advantages that color is uniform, lucuriant in design.
To achieve the above object one, the present invention provides the following technical scheme that
A kind of colour ETPU sole, raw material includes the component of following parts by weight:
10-20 parts of isoflurane chalcone diisocyanate；
20-40 parts of polyester polyol；
10-20 parts of polyether polyol；
2-5 parts of chain extender；
1-5 parts of white carbon black；
Different 1-2 parts of Masterbatch mixture of at least two colors；
The raw material of Masterbatch includes the component of following parts by weight:
25-30 parts of TPU；
30-50 parts of pigment；
1-5 parts of dispersing agent；
0.5-1.5 parts of heat stabilizer；
0.5-1.5 parts of light stabilizer；
10-20 parts of filler；
6-8 parts of compatilizer；
6-10 parts of lubricant.
By using above-mentioned technical proposal, pigment is added in TPU base-material, and compatilizer is added and increases the compatible of pigment
Property, the dispersibility of dispersing agent enhancing pigment is added, heat stabilizer and light stabilizer can resist the light of the benzene ring structure of polyurethane
Thermal oxide avoids jaundice from influencing TPU color；Replace conventional use of diphenyl methane two different using isoflurane chalcone diisocyanate
Cyanate, the defect problem of molecular structure is not present in the product worked it out, fast light, heat-resisting, oxidation resistent susceptibility is strong, is not likely to produce Huang
Become, improves product quality.
Further preferably, the dispersing agent is any in polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol
It is a kind of.
By using above-mentioned technical proposal, above-mentioned dispersing agent is organic dispersing agent, can be improved point of the pigment in TPU
Dissipate property.
Further preferably, the heat stabilizer is selected from Ca-Zn composite heat stabilizer, organo-tin het stabilizer, stearic acid
At least two in calcium, zinc stearate.
By using above-mentioned technical proposal, above-mentioned heat stabilizer thermal stability is good, is resistant to 300 DEG C when foaming of height
Temperature avoids TPU from turning to be yellow, and does not influence the mechanical property of TPU.
Further preferably, the light stabilizer is O-hydroxyl-diphenyl ketone class or bis- (2,2,6,6- tetramethyl -4- piperidines
Base) sebacic acid ester hindered amine light stabilizer.
By using above-mentioned technical proposal, the good light stability of above-mentioned light stabilizer, and the mechanical property of TPU is not influenced
Energy.
Further preferably, the filler is silica, silicon carbide, aluminium nitride, any one in barium titanate.
By using above-mentioned technical proposal, above-mentioned filler can reduce the cost of Masterbatch.
Further preferably, the lubricant be zinc stearate, it is glyceryl monostearate, any one in oleamide
Kind.
By using above-mentioned technical proposal, above-mentioned lubricant can increase the mobility of melt, be easily worked molding.
Further preferably, the polyester polyol is polyethylene glycol adipate glycol, poly adipate succinic acid ester two
Any one in alcohol, polycaprolactone polyol.
By using above-mentioned technical proposal, the cohesive energy of the ester group of above-mentioned polyester polyol is high, and TPU foaming system can be improved
The characteristics such as the mechanical property of product, wear-resisting, oil resistant.
Further preferably, the polyether polyol is polytetrahydrofuran ether glycol or polyoxypropylene polyol.
By using above-mentioned technical proposal, the low-temperature flexibility of TPU foaming product is can be improved in the presence of ether, is improved resistance to
Hydrolysis property.
To achieve the above object two, the present invention provides the following technical scheme that
A kind of preparation method of colour ETPU sole, comprising the following steps:
Isoflurane chalcone diisocyanate is put into A storage tank, stirred evenly by stirring；
Mixture B is prepared, polyester polyol, polyether polyol, chain extender, white carbon black and Masterbatch are put into B storage tank, stirring
It is uniformly mixed, repeats the above steps, obtain the mixture B of different colours；
Granulation, the mixture B of isoflurane chalcone diisocyanate and different colours is granulated respectively, the reaction temperature of granulation is
140-250 DEG C, melt pressure 4-7MPa, particle diameter 0.5-5mm, obtain the ETPU particle of different colours；
Foaming, the ETPU particle of different colours is put into kettle respectively, and physical blowing agent is added, and heating is pressurizeed, after foaming,
Discharge valve is opened, the thermoplastic polyurethane foam particle of different colours is obtained；
The thermoplastic polyurethane foam particle of different colours is injected into the mold of vapor auxiliary compression molding forming machine by molding together
Interior, then molding is passed through steam from the venthole on mold, so that thermoplastic polyurethane foam particle reexpands and clinkering is
It is whole, stop being passed through steam at this time and shed molding, foaming product continues to expand up to being full of entire mold cavity, cold through cold water
But, colour ETPU sole is made after demoulding.
By using above-mentioned technical proposal, the ETPU particle of different colours is first prepared, showed when foaming on sole
The mottled decorative pattern of different colours, between different colours will not colour contamination, then replace conventional use with isoflurane chalcone diisocyanate
Methyl diphenylene diisocyanate, the product worked it out be not present molecular structure defect problem, fast light, heat-resisting, resistance to oxidation
Performance is strong, is not likely to produce xanthochromia, improves product quality.
In conclusion compared with prior art, the invention has the following advantages:
(1) pigment is added in TPU base-material, and the compatibility that compatilizer increases pigment is added, and dispersing agent, which is added, enhances pigment
Dispersibility, heat stabilizer and light stabilizer can resist the photo-thermal oxidation of the benzene ring structure of polyurethane, jaundice avoided to influence TPU
Color；
(2) conventional use of methyl diphenylene diisocyanate, the product worked it out are replaced using isoflurane chalcone diisocyanate
It is fast light, heat-resisting, oxidation resistent susceptibility is strong there is no the defect problem of molecular structure, it is not likely to produce xanthochromia, improves product quality；
(3) it first prepares the ETPU particle of different colours, shows the mottled decorative pattern of different colours when foaming on sole, no
With will not colour contamination between color.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention will be described in detail.
Embodiment 1: a kind of colour ETPU sole, raw material includes the component of following parts by weight:
10 parts of isoflurane chalcone diisocyanate；
20 parts of polyester polyol；
20 parts of polyether polyol；
2 parts of chain extender；
1 part of white carbon black；
Different 1 part of Masterbatch mixture of at least two colors；Wherein, polyester polyol is polyethylene glycol adipate glycol,
Polyether polyol is polytetrahydrofuran ether glycol, and chain extender is ethylene glycol.
Masterbatch mixture includes 1 part of Masterbatch a and 1 part of Masterbatch b, each component of Masterbatch a and its corresponding weight
Number is as shown in table 1, and wherein pigment is carbon black, and dispersing agent is polyacrylamide, and heat stabilizer includes the calcium zinc that weight ratio is 1:1
Composite thermal stabilizer and calcium stearate, light stabilizer are O-hydroxyl-diphenyl ketone, and filler is silica, and compatilizer is polyethylene
Grafted maleic anhydride, lubricant are zinc stearate.Masterbatch b and Masterbatch a the difference is that, pigment uses cadmium red.Color
Master batch b and Masterbatch a is made using conventional screw extruding granulating process.
A kind of preparation method of colour ETPU sole, process flow as shown in Figure 1, and the following steps are included:
Isoflurane chalcone diisocyanate is put into A storage tank, stirred evenly by stirring；
Mixture B is prepared, polyester polyol, polyether polyol, chain extender, white carbon black and Masterbatch a are put into B storage tank, stirred
It mixes uniformly mixed, obtains the mixture B of black；By polyester polyol, polyether polyol, chain extender, white carbon black and Masterbatch b
B storage tank is put into, is uniformly mixed, red mixture B is obtained；
Granulation, the mixture B of isoflurane chalcone diisocyanate and different colours is injected into granulation underwater double screw extruder
It is granulated, the reaction temperature of granulation is 140 DEG C, melt pressure 4MPa, screw speed 1500r/min, and particle diameter is
0.5mm obtains the ETPU particle of different colours；
Foaming, the ETPU particle of different colours is put into kettle respectively, and physical blowing agent carbon dioxide, heating pressurization, hair is added
Steeping temperature is 150 DEG C, blow pressure 25MPa, after foaming, opens discharge valve, and the opening time is 5 seconds, obtains difference
The thermoplastic polyurethane foam particle of color；
The thermoplastic polyurethane foam particle of different colours is injected into the mold of vapor auxiliary compression molding forming machine by molding together
Interior, molding, the clamping pressure of mold is 1MPa, and 160 DEG C of steam is then passed through from the venthole on mold, and heating time is
120s stops being passed through steam at this time and sheds molding so that thermoplastic polyurethane foam particle reexpands and clinkering is whole,
Foaming product continues expansion until full of entire mold cavity, and through cold water cooling, colour ETPU sole is made after demoulding.
Embodiment 2-5: a kind of colour ETPU sole, difference from example 1 is that, each component of Masterbatch a and
Its corresponding parts by weight is as shown in table 1.
The each component and its parts by weight of Masterbatch a in 1 embodiment 1-5 of table
Embodiment 6: a kind of colour ETPU sole, difference from example 1 is that, dispersing agent is polyvinylpyrrolidone.
Embodiment 7: a kind of colour ETPU sole, difference from example 1 is that, dispersing agent is polyvinyl alcohol.
Embodiment 8: a kind of colour ETPU sole, difference from example 1 is that, heat stabilizer includes that weight ratio is
The organo-tin het stabilizer and zinc stearate of 1:1.
Embodiment 9: a kind of colour ETPU sole, difference from example 1 is that, light stabilizer be it is bis- (2,2,6,
6- tetramethyl -4- piperidyl) sebacic acid ester.
Embodiment 10: a kind of colour ETPU sole, difference from example 1 is that, filler is silicon carbide.
Embodiment 11: a kind of colour ETPU sole, difference from example 1 is that, filler is aluminium nitride.
Embodiment 12: a kind of colour ETPU sole, difference from example 1 is that, filler is barium titanate.
Embodiment 13: a kind of colour ETPU sole, difference from example 1 is that, compatilizer is styrene-Malaysia
Acid anhydride copolymer.
Embodiment 14: a kind of colour ETPU sole, difference from example 1 is that, compatilizer is polypropylene grafted
Maleic anhydride.
Embodiment 15: a kind of colour ETPU sole, difference from example 1 is that, polyester polyol is to gather oneself two
Sour butyl glycol ester diol.
Embodiment 16: a kind of colour ETPU sole, difference from example 1 is that, polyester polyol is to gather in oneself
Ester polyol.
Embodiment 17: a kind of colour ETPU sole, difference from example 1 is that, the polyether polyol is poly-
Propylene oxide polyol.
Embodiment 18: a kind of colour ETPU sole, difference from example 1 is that, the raw material of colored ETPU sole
Component including following parts by weight:
15 parts of isoflurane chalcone diisocyanate；
30 parts of polyester polyol；
15 parts of polyether polyol；
3.5 parts of chain extender；
3 parts of white carbon black；
Different 1.5 parts of Masterbatch mixture of at least two colors.
Embodiment 19: a kind of colour ETPU sole, difference from example 1 is that, the raw material of colored ETPU sole
Component including following parts by weight:
20 parts of isoflurane chalcone diisocyanate；
40 parts of polyester polyol；
10 parts of polyether polyol；
5 parts of chain extender；
5 parts of white carbon black；
Different 2 parts of Masterbatch mixture of at least two colors.
Embodiment 20: a kind of colour ETPU sole, difference from example 1 is that, granulation specifically includes: by different fluorine
The mixture B of that ketone diisocyanate and different colours, which is injected into granulation underwater double screw extruder, to be granulated, granulation
Reaction temperature is 200 DEG C, melt pressure 6MPa, screw speed 1500r/min, and particle diameter 5mm obtains different colours
ETPU particle.
Embodiment 21: a kind of colour ETPU sole, difference from example 1 is that, granulation specifically includes: by different fluorine
The mixture B of that ketone diisocyanate and different colours, which is injected into granulation underwater double screw extruder, to be granulated, granulation
Reaction temperature is 250 DEG C, melt pressure 7MPa, screw speed 1500r/min, and particle diameter 3mm obtains different colours
ETPU particle.
Comparative example 1: a kind of colour ETPU sole, difference from example 1 is that, it is not added in the raw material of Masterbatch
Polyacrylamide.
Comparative example 2: a kind of colour ETPU sole, difference from example 1 is that, it is not added in the raw material of Masterbatch
Research of Grafting Malaic Anhydride Onto Polyethylene.
Comparative example 3: a kind of colour ETPU sole, difference from example 1 is that, it is not added in the raw material of Masterbatch
Polyacrylamide and Research of Grafting Malaic Anhydride Onto Polyethylene.
Comparative example 4: a kind of colour ETPU sole, difference from example 1 is that, use two isocyanide of diphenyl methane
Acid esters replaces isoflurane chalcone diisocyanate.
Comparative example 5: a kind of colour ETPU sole, difference from example 1 is that, heat stabilizer is not added.
Comparative example 6: a kind of colour ETPU sole, difference from example 1 is that, light stabilizer is not added.
Test a chromatism test
Test specimen: using the indsole prepared in embodiment 1-21 as test specimen 1-21, using what is obtained in comparative example 1-6
Indsole is as control sample 1-6.
Test method: in standard multiple light courcess under colored lights irradiation condition, test specimen 1-21 and control sample 1-6 is distinguished
Visual colorimetry is carried out with standard sample, each sample test three times, is averaged, and the score range that scores is 1-5 points；Scoring mark
Quasi-: it is 5 points that colour contamination, color be not uniform, and spot edge slightly color difference is 4-4.9 points, and the joint of adjacent spots slightly colour contamination is
3-3.9 points, the more serious joint colour contamination and color difference of adjacent spots is 2-2.9 points, and spot colour contamination is serious, color difference is evident as 1-
1.9 point.
Test result: the test result of test specimen 1-21 and control sample 1-6 are as shown in table 2.As shown in Table 2, it tests
The color difference of sample 1-21 scores at 4.8 points or more, and control sample 1-3 is at 2 points hereinafter, illustrate compatible in the application
Agent, dispersing agent are used cooperatively the dispersibility that pigment can be remarkably reinforced, and heat stabilizer and light stabilizer can resist polyurethane
The photo-thermal of benzene ring structure aoxidizes, and jaundice is avoided to influence TPU color.
The appraisal result of table 2 test specimen 1-22 and control sample 1-6
Test two non-yellowing tests
Test specimen: using the indsole prepared in embodiment 1-21 as test specimen 1-21, using what is obtained in comparative example 1-6
Indsole is as control sample 1-6.
Test method: the xanthochromia degree of sole is carried out according to A method in " HGT3689-2001 footwear non-yellowing test method "
Dependence test shines test specimen 1-21 and control sample 1-6 under the light bulb that the wavelength of ultraviolet lamp light wave is 280~400nm
The stipulated time is penetrated 6 hours, then in the case where standard multiple light courcess is to colored lights with the direct covered part of visually rank sample of gray scale
Corresponding xanthochromia series, is accurate to 0.5 grade.
The characterizing method of color inhibition under high temperature: test specimen 1-21 and control sample 1-6 is put respectively in 100 DEG C of baking ovens
It sets 48 hours, uses gray scale visually rank xanthochromia series in the case where standard multiple light courcess is to colored lights with untreated sole sample,
It is accurate to 0.5 grade.
Test result: the test result of test specimen 1-21 and control sample 1-6 are as shown in table 3.As shown in Table 3, it tests
The color inhibition grade of sample 1-21 is at 4 grades or more, and the color inhibition grade of control sample 4 is 2 grades, the color inhibition of control sample 5
(high temperature) grade is 1.5 grades, and color inhibition (ultraviolet light) grade of control sample 6 is 1.5 grades.Illustrate the present invention in TPU base-material
Add pigment, and be added compatilizer increase pigment compatibility, be added dispersing agent enhancing pigment dispersibility, heat stabilizer and
Light stabilizer can resist the photo-thermal oxidation of the benzene ring structure of polyurethane, and jaundice is avoided to influence TPU color；By using different fluorine that
Ketone diisocyanate replaces conventional use of methyl diphenylene diisocyanate, and there is no molecular structure to lack for the product worked it out
The problem of falling into, it is fast light, heat-resisting, oxidation resistent susceptibility is strong, it is not likely to produce xanthochromia, improves product quality.
The test result of table 3 test specimen 1-21 and control sample 1-6
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
For those of ordinary skill, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of colour ETPU sole, which is characterized in that its raw material includes the component of following parts by weight:
10-20 parts of isoflurane chalcone diisocyanate；
20-40 parts of polyester polyol；
10-20 parts of polyether polyol；
2-5 parts of chain extender；
1-5 parts of white carbon black；
Different 1-2 parts of Masterbatch mixture of at least two colors；
The raw material of Masterbatch includes the component of following parts by weight:
25-30 parts of TPU；
30-50 parts of pigment；
1-5 parts of dispersing agent；
0.5-1.5 parts of heat stabilizer；
0.5-1.5 parts of light stabilizer；
10-20 parts of filler；
6-8 parts of compatilizer；
6-10 parts of lubricant.
2. colour ETPU sole according to claim 1, which is characterized in that the dispersing agent is selected from polyacrylamide, gathers
Any one in vinylpyrrolidone, polyvinyl alcohol.
3. colour ETPU sole according to claim 1, which is characterized in that it is steady that the heat stabilizer is selected from Ca Zn composite heat
Determine agent, organo-tin het stabilizer, calcium stearate, at least two in zinc stearate.
4. colour ETPU sole according to claim 1, which is characterized in that the light stabilizer is O-hydroxyl-diphenyl ketone
Class or bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacic acid ester hindered amine light stabilizers.
5. colour ETPU sole according to claim 1, which is characterized in that the filler is silica, silicon carbide, nitrogen
Change aluminium, any one in barium titanate.
6. colour ETPU sole according to claim 1, which is characterized in that the compatilizer is polycthylene grafted maleic acid
Acid anhydride, styrene-maleic anhydride copolymer, any one in polypropylene grafted maleic anhydride.
7. colour ETPU sole according to claim 1, which is characterized in that the lubricant is zinc stearate, stearic acid
Any one in monoglyceride, oleamide.
8. colour ETPU sole according to claim 1, which is characterized in that the polyester polyol is polyadipate second two
Alcohol esterdiol, polybutylene glyool adipate, any one in polycaprolactone polyol.
9. colour ETPU sole according to claim 1, which is characterized in that the polyether polyol is polytetrahydrofuran ether
Glycol or polyoxypropylene polyol.
10. a kind of preparation method of colour ETPU sole, which comprises the following steps:
Isoflurane chalcone diisocyanate is put into A storage tank, stirred evenly by stirring；
Mixture B is prepared, polyester polyol, polyether polyol, chain extender, white carbon black and Masterbatch are put into B storage tank, stirring
It is uniformly mixed, repeats the above steps, obtain the mixture B of different colours；
Granulation, the mixture B of isoflurane chalcone diisocyanate and different colours is granulated respectively, the reaction temperature of granulation is
140-250 DEG C, melt pressure 4-7MPa, particle diameter 0.5-5mm, obtain the ETPU particle of different colours；
Foaming, the ETPU particle of different colours is put into kettle respectively, and physical blowing agent is added, and heating is pressurizeed, after foaming,
Discharge valve is opened, the thermoplastic polyurethane foam particle of different colours is obtained；
The thermoplastic polyurethane foam particle of different colours is injected into the mold of vapor auxiliary compression molding forming machine by molding together
Interior, then molding is passed through steam from the venthole on mold, so that thermoplastic polyurethane foam particle reexpands and clinkering is
It is whole, stop being passed through steam at this time and shed molding, foaming product continues to expand up to being full of entire mold cavity, cold through cold water
But, colour ETPU sole is made after demoulding.
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| WO2021072665A1 (en) * | 2019-10-16 | 2021-04-22 | 加久企业股份有限公司 | Tpu foam sole manufacturing process and product thereof |
| CN113549339A (en) * | 2021-08-05 | 2021-10-26 | 温州市荣奇鞋业有限公司 | Leisure shoe sole and preparation method thereof |
| CN115584116A (en) * | 2021-12-23 | 2023-01-10 | 上海涵点科技有限公司 | Preparation method and application of environment-friendly inorganic powder dispersant |
| CN117866452A (en) * | 2023-06-15 | 2024-04-12 | 长大市政工程(广东)有限公司 | Environment-friendly color asphalt pavement material and preparation method thereof |
| CN115584116B (en) * | 2021-12-23 | 2024-10-25 | 上海涵点新材料有限公司 | Preparation method and application of environment-friendly inorganic powder dispersing agent |
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Application publication date: 20190326 |